CN103429660A - Thermoplastic resin composition and molded article using same - Google Patents
Thermoplastic resin composition and molded article using same Download PDFInfo
- Publication number
- CN103429660A CN103429660A CN2011800693442A CN201180069344A CN103429660A CN 103429660 A CN103429660 A CN 103429660A CN 2011800693442 A CN2011800693442 A CN 2011800693442A CN 201180069344 A CN201180069344 A CN 201180069344A CN 103429660 A CN103429660 A CN 103429660A
- Authority
- CN
- China
- Prior art keywords
- thermoplastic resin
- resin composition
- carbon black
- structural unit
- liquid crystalline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3804—Polymers with mesogenic groups in the main chain
- C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
- H01B3/421—Polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
Abstract
A thermoplastic resin composition which is obtained by blending 0.1-20 parts by weight of carbon black per 100 parts by weight of a thermoplastic resin. The thermoplastic resin composition is characterized in that the carbon black is dispersed in the thermoplastic resin composition so as to have a maximum particle diameter of 50 [mu]m or less.
Description
Technical field
The products formed that the present invention relates to the thermoplastic resin composition and used this thermoplastic resin composition.Relate in further detail the thermoplastic resin composition who comprises carbon black of the purposes that is preferred for requiring black and the thin molded article that has used this thermoplastic resin composition.
Background technology
In recent years, more and more higher for the requirement of the high performance of plastics, thereby developed in a large number the polymkeric substance with various new capabilities, supply market, particularly thermoplastic resin are widely used owing to take the easy processibility that injection molding is representative.Wherein painted for goods are deceived, generally added carbon black, thereby in the various parts such as automobile, electric and electronic, precision optical machinery, business machine for purposes widely.
Yet, in the situation that use general carbon black, there is the distinctive agglomeration of carbon black to be easy to produce, the carbon black agglomeration becomes the strength decreased of reason, the problems such as defective insulation.
As black painted thermoplastic resin composition, following such resin combination is disclosed.For example disclose, with respect to polyamide resin, contained (i) ethylenebis stearic amide and (ii) polymeric amide that carbon black that particle diameter is 8～120 μ m forms composition (for example, with reference to patent documentation 1) for molded-in-color.In addition, disclose with respect to polyphenylene sulfide, added the polyphenylene sulfide (for example, with reference to patent documentation 2) that the above carbon black of pH8 forms.Yet, in these resin combinations, the dispersion of carbon black is insufficient, for thin-walled property in recent years products formed, can cause defective insulation.
On the other hand, in thermoplastic resin, being arranged in parallel of molecular chain received publicity having aspect excellent mobility, thermotolerance, low gaseousness and mechanical properties as the anisotropic liquid-crystalline resin of the display optical of its feature.
Liquid-crystalline resin, be suitable for the material of the electrical and electronic parts of thinner wall section or complicated shape as the above-mentioned feature of performance, and for for example, junctor, camera module, rly., switch, coil bobbin etc.Yet in the groove, the article shape more and more requirement of thin-walled property is strong, even for above-mentioned electrical and electronic parts, also requires the raising of further physical strength, mobility as resin combination for compactization in recent years.The fraction defectives such as the random ejaculation in injection molding operation on the other hand, reduce, prevent requirement that resin combination powder in assembling procedure comes off etc. while producing to the quality aspect from molded surface, and also year annual variation is tight.For example, about junctor, products formed wall thickness between metal terminal is more and more in thin-walled property, the difference of the parts from the situation for simplifying assembling multiple types parts, for the easiness of the image analysis of the visual inspection of parts itself, the liquid-crystalline resin that has required to deceive painted.In addition, about opticses such as camera modules, the viewpoint of the mobility of getting married and start a new life, opacifying property is set out, and when requiring black painted liquid-crystalline resin, is strict with and prevents that the resin combination powder that becomes the bad reason of image from coming off from the products formed surface.
As black painted liquid crystalline resin composition, in addition, following such resin combination is disclosed.For example disclose, with respect to liquid crystalline polyester 100 weight parts, the liquid crystalline resin composition (for example, with reference to patent documentation 3) that the carbon black that to contain pH be 3.5～10 forms.In addition, disclose with respect to thermoplastic resin 100 weight parts, containing dibutyl phthalate (below, be called DBP) adsorptive capacity is thermoplastic resin composition's (for example,, with reference to patent documentation 4) that following carbon black 0.01～10 weight part of 150ml/100g forms.In addition, disclose with respect to liquid crystalline polyester 100 weight parts, coordinating (i) median size is 5～20nm, and the DBP absorbed dose is 60～200cm
3Carbon black 0.1～10 weight part of/100g and the liquid crystalline polyester resin composition (for example,, with reference to patent documentation 5) that (ii) fibrous and/or tabular inorganic fill material 0～180 weight part forms.Yet these resin combinations cause that the agglomeration of carbon black generates, in the situation that for products formeds such as junctors, the problem of the defective insulation that the agglomeration by carbon black causes occurs between the metal terminal had at thin-walled property.Defective insulation is clear and definite problem after the goods assembling, therefore, in the situation that the defective insulation generation is large on the impact of goods integral body, requires to improve.
Therefore, as the liquid crystalline resin composition of insulativity, thermotolerance, mechanical characteristics excellence, following such liquid crystalline resin composition (for example,, with reference to patent documentation 6) is disclosed.This liquid crystalline resin composition is for coordinating (i) liquid-crystalline resin 100 weight parts, carbon black 1～10 weight part of (ii) primary particle size 10～50nm and the liquid crystalline resin composition that (iii) talcum 0.1～10 weight part of median diameter 1～20 μ m forms.In this liquid-crystalline resin, carbon black is to disperse below median size 50 μ m.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication sho 61-55146 communique
Patent documentation 2: TOHKEMY 2000-230120 communique
Patent documentation 3: Japanese kokai publication hei 07-196894 communique
Patent documentation 4: Japanese kokai publication hei 10-101945 communique
Patent documentation 5: TOHKEMY 2001-279066 communique
Patent documentation 6: TOHKEMY 2009-179763 communique
Summary of the invention
Invent problem to be solved
Yet, even use aforesaid method, also can have the carbon black that surpasses 50 μ m in maximum particle diameter, in recent years at thin-walled property more metal terminal between to maintain insulativity be difficult.In addition, the resistance when thinner wall section that is created on products formed of carbon agglomeration becomes resin flows, be easy to become the reason that causes obstruction, and bad being easy to such as random ejaculation during injection molding occurs.In addition, the agglomeration of carbon black becomes reason and the roughen of products formed surface, and in assembling procedure etc., the resin combination powder comes off from the products formed surface sometimes.The present invention solves such problem of the prior art and is studied and realizes as purpose.; the purpose of this invention is to provide thin wall flow dynamic stability excellence; even also can obtain the products formed of insulativity excellence in the purposes of the thinner wall section with requirement black, and can suppress the thermoplastic resin composition that the resin combination powder comes off from the products formed surface.
For solving the means of problem
The present invention proposes at least a portion that solves above-mentioned problem, and embodiments of the present invention can comprise at least a portion of following enumerated formation.
(1) a kind of thermoplastic resin composition, coordinate carbon black 0.1～20 weight part to form with respect to thermoplastic resin 100 weight parts.Carbon black is to be dispersed in this thermoplastic resin composition below maximum particle diameter 50 μ m.
(2) above-mentioned (1) described thermoplastic resin composition.For such thermoplastic resin composition, the primary particle size of above-mentioned carbon black is 70～200nm.For such thermoplastic resin composition, the DBP absorbed dose a1 (ml/100g) of carbon black is 0.5～1.5 (ml/100gnm) with the ratio (a1/a2) of primary particle size a2 (nm).
Wherein, for above-mentioned (1) described thermoplastic resin composition, above-mentioned primary particle size can be less than 70nm.In addition, above-mentioned primary particle size can surpass 200nm.
For above-mentioned (1) described thermoplastic resin composition, above-mentionedly than (a1/a2), can be less than 0.5 (ml/100gnm).In addition, above-mentionedly than (a1/a2), can surpass 1.5 (ml/100gnm).
(3) above-mentioned (1) or (2) described thermoplastic resin composition.For such thermoplastic resin composition, the specific surface area obtained by BET formula low-temperature nitrogen adsorption method of above-mentioned carbon black is 10～40 (m
2/ g).
Wherein, for above-mentioned (1) or (2) described thermoplastic resin composition, above-mentioned specific surface area can be less than 10 (m
2/ g).In addition, for above-mentioned (1) or (2) described thermoplastic resin composition, above-mentioned specific surface area can surpass 40 (m
2/ g).
(4) according to the described thermoplastic resin composition of any one of (1)～(3), it is characterized in that, above-mentioned thermoplastic resin is for forming the liquid crystalline polyester resin of anisotropy melting phase.
Wherein, for the described thermoplastic resin composition of any one of (1)～(3), can be for not forming the liquid crystalline polyester resin of anisotropy melting phase.
(5) above-mentioned liquid crystalline polyester resin is by following structural unit (I), (II), (III), (IV) and above-mentioned (4) described thermoplastic resin composition of (V) forming.For such thermoplastic resin composition, structural unit (I) with respect to structural unit (I), (II) and (III) add up to 65～80 % by mole.Structural unit (II) with respect to structural unit (II) and (III) add up to 55～85 % by mole.Structural unit (IV) with respect to structural unit (IV) and (V) add up to 50～95 % by mole.
Wherein, for above-mentioned (4) described thermoplastic resin composition, structural unit (I) can be less than 65 % by mole with respect to structural unit (I), (II) and total (III).In addition, structural unit (I) can be over 80 % by mole with respect to structural unit (I), (II) and total (III).
For above-mentioned (4) described thermoplastic resin composition, structural unit (II) can be less than 55 % by mole with respect to structural unit (II) and total (III).In addition, structural unit (II) can be over 85 % by mole with respect to structural unit (II) and total (III).
For above-mentioned (4) described thermoplastic resin composition, structural unit (IV) can be less than 50 % by mole with respect to structural unit (IV) and total (V).In addition, structural unit (IV) can be over 95 % by mole with respect to structural unit (IV) and total (V).
In addition, the liquid crystalline polyester resin that forms above-mentioned (4) described thermoplastic resin composition can not contain said structure unit (I), (II), (III), (IV) and at least a portion (V).
(6) according to the described thermoplastic resin composition of any one of (1)～(5), its 100 weight parts of total with respect to above-mentioned thermoplastic resin and above-mentioned carbon black, also be combined with inorganic fill material 1～200 weight part.
Wherein, for the described thermoplastic resin composition of any one of above-mentioned (1)～(5), the use level of above-mentioned inorganic fill material can be less than 1 weight part.In addition, for the described thermoplastic resin composition of any one of above-mentioned (1)～(5), the use level of above-mentioned inorganic fill material can surpass 200 weight parts.
(7) be supplied to biaxial extruder to major general's thermoplastic resin and carbon black and carry out the method that melting mixing is manufactured the described thermoplastic resin composition of any one of (1)～(6).Manufacture method for such thermoplastic resin composition, with respect to the total length (L) from raw material input position (L0) to drain position of biaxial extruder, what make thermoplastic resin and carbon black is below 15% of the residence time of biaxial extruder total length (total holdup time) from dropping into position (L0) to the residence time between 3L/10 (residence time at initial stage).In addition, for such thermoplastic resin composition's manufacture method, making from 3L/10 to the maximum shear speed between drain position was 1000～10000 (/ seconds), carried out melting mixing.
Wherein, for the described thermoplastic resin composition's of any one who manufactures above-mentioned (1)～(6) method, the above-mentioned residence time at initial stage can surpass 15% of the total holdup time.
For the described thermoplastic resin composition's of any one who manufactures above-mentioned (1)～(6) method, can be less than for 1000 (/ seconds) from above-mentioned 3L/10 to the maximum shear speed between drain position.In addition, can surpass for 10000 (/ seconds) from above-mentioned 3L/10 to the maximum shear speed between drain position.
In addition, as the described thermoplastic resin composition's of any one who manufactures (1)～(6) method, can adopt and be supplied to biaxial extruder to major general's thermoplastic resin and carbon black and carry out the direction that the method for melting mixing is different.
(8) a kind of products formed, the described thermoplastic resin composition's moulding of its any one by above-mentioned (1)～(6) obtains.
(9), according to above-mentioned (8) described products formed, it has the following part of wall thickness 0.1mm.
The effect of invention
The thermoplastic resin composition's of embodiments of the present invention thin wall flow dynamic stability is high, can obtain the insulativity excellence, and has suppressed the products formed that the resin combination powder comes off from the products formed surface.
The accompanying drawing explanation
Fig. 1 is for showing the insulativity in embodiment, the sketch chart that the thin-walled test film is used in the evaluation of thin wall flow dynamic stability.
Fig. 2 is for showing the insulativity evaluation that the has been coated with conductive paste sketch chart of thin-walled test film.
Fig. 3 is the observation by light microscope photo by the grain section of embodiment 1 acquisition.
Fig. 4 is the observation by light microscope photo by the grain section of comparative example 1 acquisition.
Embodiment
The thermoplastic resin used in embodiments of the present invention, be if heating show mobility, utilizes the synthetic resins that it can forming process.As its concrete example, can enumerate polyphenylene oxide, polyphenylene sulfide, polyamide-based resin (nylon 6, nylon 66 etc.), polyester based resin (polyethylene terephthalate, polybutylene terephthalate, PBN etc.), polyoxymethylene, acrylonitrile-butadiene-styrene copolymer, polystyrene, liquid crystalline polyester etc.
Wherein, from viewpoints such as mechanical properties, formabilities, be preferably polyamide-based resin, polybutylene terephthalate, polyoxymethylene, the liquid crystalline polyesters such as polyphenylene sulfide, nylon 6, nylon 66.
Particularly in the situation that the liquid crystalline polyester resin composition of thin-walled mobility excellence for thinner wall section goods how, therefore can be expected the application's effect due in a large number most.
Below, the situation of having used liquid crystalline polyester resin in thermoplastic resin is described.
(A) liquid crystalline polyester resin is to comprise the structural unit be selected from such as in aromatic series oxygen base carbonyl unit, aromatic series and/or aliphatics dioxy base unit, aromatic series and/or aliphatics dicarbapentaborane unit etc., and forms the liquid crystalline polyester resin of anisotropy melting phase.
As aromatic series oxygen base carbonyl unit, for example can enumerate, the structural unit generated by P-hydroxybenzoic acid, 6-Hydroxy-2-naphthoic acid etc., be preferably P-hydroxybenzoic acid.As aromatic series and/or aliphatics dioxy base unit, for example can enumerate, by 4,4 '-dihydroxybiphenyl, quinhydrones, 3,3 ', 5,5 '-tetramethyl--4,4 '-dihydroxybiphenyl, tertiary butylated hydroquinone, phenyl quinhydrones, 2,6-dihydroxy naphthlene, 2,7-dihydroxy naphthlene, 2, two (4-hydroxy phenyl) propane and 4 of 2-, 4 '-dihydroxydiphenyl ether, ethylene glycol, 1, ammediol, 1, the structural unit that 4-butyleneglycol etc. generate, be preferably 4,4 '-dihydroxybiphenyl, quinhydrones.As aromatic series and/or aliphatics dicarbapentaborane unit, for example can enumerate, by terephthalic acid, m-phthalic acid, NDA, 4,4 '-phenylbenzene dioctyl phthalate, 1, two (phenoxy group) ethane-4 of 2-, 4 '-dioctyl phthalate, 1, two (2-chlorophenoxy) ethane-4 of 2-, 4 '-dioctyl phthalate, 4, the structural unit that 4 '-diphenyl ether dioctyl phthalate, hexanodioic acid, sebacic acid etc. generate, be preferably terephthalic acid, m-phthalic acid.
As the concrete example of (A) liquid crystalline polyester resin, can enumerate the liquid crystalline polyester resin that the structural unit that generated by P-hydroxybenzoic acid and 6-Hydroxy-2-naphthoic acid forms, the structural unit generated by P-hydroxybenzoic acid, the structural unit generated by 6-Hydroxy-2-naphthoic acid, by aromatic dihydroxy compound, the liquid crystalline polyester resin that the structural unit that aromatic dicarboxylic acid and/or aliphatic dicarboxylic acid generate forms, the structural unit generated by P-hydroxybenzoic acid, by 4, the structural unit that 4 '-dihydroxybiphenyl generates, by terephthalic acid, aromatic dicarboxylic acid and/or the hexanodioic acids such as m-phthalic acid, the liquid crystalline polyester resin that the structural unit that the aliphatic dicarboxylic acids such as sebacic acid generate forms, the structural unit generated by P-hydroxybenzoic acid, by 4, the structural unit that 4 '-dihydroxybiphenyl generates, the structural unit generated by quinhydrones, by terephthalic acid, aromatic dicarboxylic acid and/or the hexanodioic acids such as m-phthalic acid, the liquid crystalline polyester resin that the structural unit that the aliphatic dicarboxylic acids such as sebacic acid generate forms, the structural unit generated by P-hydroxybenzoic acid, the structural unit generated by ethylene glycol, the liquid crystalline polyester resin that the structural unit generated by terephthalic acid and/or m-phthalic acid forms, the structural unit generated by P-hydroxybenzoic acid, the structural unit generated by ethylene glycol, by 4, the structural unit that 4 '-dihydroxybiphenyl generates, by terephthalic acid and/or hexanodioic acid, the liquid crystalline polyester resin that the structural unit that the aliphatic dicarboxylic acids such as sebacic acid generate forms, the structural unit generated by P-hydroxybenzoic acid, the structural unit generated by ethylene glycol, the structural unit generated by aromatic dihydroxy compound, by terephthalic acid, m-phthalic acid, the liquid crystalline polyester resin that the structural unit that the aromatic dicarboxylic acids such as NDA generate forms, the structural unit generated by 6-Hydroxy-2-naphthoic acid, by 4, the structural unit that 4 '-dihydroxybiphenyl generates, the liquid crystalline polyester resin that the structural unit generated by NDA forms etc.They can contain two or more.
In these liquid crystalline polyester resins, be preferably by following structural unit (I), (II), (III), (IV) and the liquid crystalline polyester resin that (V) forms.Such liquid crystalline polyester resin can make the dispersiveness of carbon black further improve.In addition, by being combined with manufacture method described later, thereby can carry out more well the dispersion of the carbon black in liquid crystalline polyester resin composition.
Said structure unit (I) means the structural unit generated by P-hydroxybenzoic acid, structural unit (II) means by 4, the structural unit that 4 '-dihydroxybiphenyl generates, structural unit (III) means the structural unit generated by quinhydrones, structural unit (IV) means the structural unit generated by terephthalic acid, and structural unit (V) means the structural unit generated by m-phthalic acid.
Structural unit (I), with respect to structural unit (I), (II) and total (III), is preferably 65～80 % by mole.Particularly from the dispersiveness raising of carbon black, more preferably 68～78 % by mole.
In addition, structural unit (II), with respect to structural unit (II) and total (III), is preferably 55～85 % by mole.Particularly, from the further raising of dispersiveness of carbon black, more preferably 55～78 % by mole, most preferably be 58～73 % by mole.
In addition, structural unit (IV), with respect to structural unit (IV) and total (V), is preferably 50～95 % by mole.Particularly, from the further raising of dispersiveness of carbon black, more preferably 55～90 % by mole, most preferably be 60～85 % by mole.
Structural unit (II) and total (III) and total (IV) and (V) preferably are essentially etc. mole.Here, so-called " be essentially wait mole ", the structural unit that means to remove as formation the main polymer chain of end is grade mole.Therefore, in the situation that connect the structural unit form end, differ in being also contained in and be decided to be equimolar mode, also can meet the important document of " be essentially etc. mole ".For the terminal group of telomerized polymer, can add dicarboxylic acid composition or dihydroxyl composition superfluously.
The above-mentioned liquid crystalline polyester resin used in embodiments of the present invention can obtain by the condensation methods of known polyester.For example, preferably can enumerate following manufacture method.
(1), by acetoxy-benzoic acid and 4,4 '-diacetoxy biphenyl, diacetoxy benzene and terephthalic acid, m-phthalic acid are manufactured the method for liquid crystalline polyester resin by the desacetoxy polycondensation.
(2) make diacetyl oxide and P-hydroxybenzoic acid and 4,4 '-dihydroxybiphenyl, quinhydrones and terephthalic acid, m-phthalic acid are reacted, and by after phenol hydroxyl acylations, manufacture the method for liquid crystalline polyester resin by the desacetoxy polycondensation.
(3) by the phenylester and 4 of P-hydroxybenzoic acid, the diphenyl of 4 '-dihydroxybiphenyl, quinhydrones and terephthalic acid, m-phthalic acid is manufactured the method for liquid crystalline polyester resin by de-phenol polycondensation.
(4) diphenyl carbonate of specified amount is reacted with aromatic dicarboxylic acids such as P-hydroxybenzoic acid and terephthalic acid, m-phthalic acids, after making diphenyl respectively, add 4, the aromatic dihydroxy compound such as 4 '-dihydroxybiphenyl, quinhydrones, manufacture the method for liquid crystalline polyester resin by de-phenol polycondensation.
In embodiments of the present invention, when by the desacetoxy polycondensation, manufacturing liquid crystalline polyester resin, preferably under reduced pressure reaction at the temperature of liquid crystalline polyester resin melting, the melt phase polycondensation that polycondensation is completed.For example can enumerate; by the P-hydroxybenzoic acid of specified amount, 4; 4 '-dihydroxybiphenyl, quinhydrones, terephthalic acid, m-phthalic acid and diacetyl oxide are added in reaction vessel; under nitrogen atmosphere, while stirring, heat and after making glycoloyl; be warming up to the melt temperature of liquid crystalline polyester resin, by decompression, carry out the method that polycondensation completes reaction.Above-mentioned reaction vessel can possess agitating vane, in addition, can possess the pipe of distillating, and in addition, bottom can possess relief outlet.
The polymkeric substance of gained, can be at the temperature of its melting for example be forced into approximately 1.0kg/cm in by reaction vessel
2(0.1MPa), by the relief outlet strip ground arranged in the reaction vessel bottom, discharged.Melt phase polycondensation is the method that is conducive to manufacture uniform polymkeric substance, can obtain the polymkeric substance of gas generated excellence still less, therefore preferably.
Even the polycondensation catalyst-free of liquid crystalline polyester resin also can carry out, but also the metallic compounds such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, ANTIMONY TRIOXIDE SB 203 99.8 PCT, MAGNESIUM METAL can be used as catalyzer.
In embodiments of the present invention, the content of each structural unit can be calculated as follows: liquid crystalline polyester is measured to NMR (nucleus magnetic resonance) test tube, and (for example, Pentafluorophenol/deuterium is for tetrachloroethane-d to be dissolved in the soluble solvent of liquid crystalline polyester
2Mixed solvent), in, carry out
1The H-NMR spectrometry, origin comes from the peak area ratio of each structural unit and calculates.
In embodiments of the present invention, fusing point (Tm) can be measured by differential scanning calorimeter.Also can calculate as follows: after the observation of the endotherm peak temperature (Tm1) observed when liquid crystalline polyester resin is measured from room temperature under the Elevated Temperature Conditions of 40 ℃/minute, after the temperature of Tm1+20 ℃ keeps 5 minutes, temporarily be cooled to room temperature under the cooling conditions of 20 ℃/minute, the endotherm peak temperature (Tm2) observed while again measuring under the Elevated Temperature Conditions of 20 ℃/minute is calculated as fusing point (Tm).
In addition, the melt viscosity of the liquid crystalline polyester resin in embodiments of the present invention is preferably 1～200Pas, and more preferably 10～200Pas, be particularly preferably 10～100Pas.In addition, under the condition that melt viscosity is fusing point at liquid crystalline polyester resin+10 ℃, velocity of shear 1, the value of measuring by high formula fluidity test machine under the condition of 000/s.
The thermoplastic resin composition of embodiments of the present invention is for coordinating carbon black 0.1～20 weight part to form with respect to above-mentioned thermoplastic resin 100 weight parts.In the situation that the content of carbon black is less than 0.1 weight part, the dispersiveness of carbon black reduces, and the thin wall flow dynamic stability reduces, and in addition, obtains desired degree of blackness and becomes difficulty.More than being preferably 1.0 weight parts.On the other hand, in the situation that the content of carbon black surpasses 20 weight parts, except the reduction of thin wall flow dynamic stability, by thermoplastic resin composition's moulding and the insulativity of products formed reduce.Be preferably below 10 weight parts.
The thermoplastic resin composition of embodiments of the present invention is characterised in that, carbon black is to be dispersed in the thermoplastic resin composition below maximum particle diameter 50 μ m.Here so-called dispersion, refer to carbon black carefully be dispersed in comprise thermoplastic resin mutually in state.The state of carbon black to disperse below maximum particle diameter 50 μ m, refer to comprise thermoplastic resin mutually in, carbon black is micro-decentralized.Even in the situation that carbon black is to disperse below median size 50 μ m, if mixing, the carbon black agglomeration part that particle diameter is large exists, such agglomeration also can become the mobile resistance that causes thinner wall section when moulding, the reason of obstruction, or becomes the reason that the resin combination powder comes off from the products formed surface.Therefore, embodiments of the present invention are conceived to the maximum particle diameter of carbon black, by the maximum particle diameter that makes the carbon black in composition, be below 50 μ m, thereby can make thermoplastic resin composition's thin wall flow dynamic stability and by their moulding and the insulativity of products formed improve, suppress the resin combination powder and come off from the products formed surface.The maximum particle diameter of carbon black is preferably below 40 μ m, more preferably below 30 μ m.In addition, in embodiments of the present invention, the maximum particle diameter of the carbon black in the thermoplastic resin composition, can observe thermoplastic resin composition's particle or the total 10cm in products formed cross section with 500～1000 times of multiplying powers by using opticmicroscope
2, obtain the length of the major diameter part of the maximum particle in the offspring of the carbon black of observing and calculate.
The preferred primary particle size of the carbon black used in embodiments of the present invention is 70～200nm.Carbon black is according to the size of primary particle and the easness difference of aggegation, the little tendency that the aggegation of being easy to is arranged of primary particle size.In embodiments of the present invention, by the primary particle size that makes carbon black, be more than 70nm, thereby can make the dispersiveness of the carbon black in the thermoplastic resin composition improve, make carbon black in composition easily to disperse below maximum particle diameter 50 μ m.Therefore, can make the thin wall flow dynamic stability of resin combination and the insulativity of products formed further improve, further reduce the resin combination powder and come off from the products formed surface.More preferably more than 80nm.In addition, from reducing, be used for the viewpoint that obtains the content of desired degree of blackness and maintain the high mechanical strength of products formed, be preferably below 200nm, more preferably below 150nm, more preferably below 120nm.
In addition, the primary particle size of the carbon black in embodiments of the present invention, refer to and use the determination of electron microscopy diameter, the value that arithmetical mean obtains, the method that the Carbon Black yearbook No.48 (1998) that can adopt carbon black association distribution puts down in writing in is p.114 obtained.More specifically, can observe carbon blacks with 20000 times of multiplying powers by using transmission electron microscope, measure the diameter of 50 carbon black particles arbitrarily, obtain it and count average and calculate.
In addition, in embodiments of the present invention, the DBP absorbed dose a1 (ml/100g) of carbon black is preferably 0.5～1.5 (ml/100gnm) with the ratio (a1/a2) of primary particle size a2 (nm).The DBP absorbed dose be the state that fuses each other of carbon black primary particle (assemble, development degree aggregate), the index of so-called " structure ", its absorbed dose by the dibutyl phthalate of every 100g carbon black is carried out the quantification structure.The ratio (a1/a2) of DBP absorbed dose and primary particle size means the development degree of structure of the per unit length of primary particle size, except the scope that the primary particle size of each carbon black is 70～200nm, preferably and deposit the scope that the ratio (a1/a2) with the DBP absorbed dose is 0.5～1.5 (ml/100gnm).That is, in the carbon black of the scope that primary particle size is 70～200nm, if value (a1/a2) is that more than 0.5 (ml/100gnm), the dispersiveness of carbon black further improves.More preferably more than 0.80 (ml/100gnm).On the other hand, if value (a1/a2) is below 1.5 (ml/100gnm), can be suppressed in the thermoplastic resin composition and forms conductive path by structure, with higher level, maintain insulativity.In addition, be easy to obtain desired degree of blackness.More preferably below 1.40 (ml/100gnm).
In addition, the DBP absorbed dose in embodiments of the present invention, the method that can adopt JIS K6217 (2001) to put down in writing is obtained.
In addition, the BET specific surface area of carbon black is preferably 10～40 (m
2/ g).The BET specific surface area, refer to the surface-area of the per unit weight of obtaining by the absorption of non-active gas.10 (m if
2/ g), more than, can reduce for obtaining the content of desired degree of blackness.15 (m more preferably
2/ g) more than.In addition, 40 (m if
2/ g), below, can make the dispersiveness of carbon black further improve.35 (m more preferably
2/ g) below.
In addition, the BET specific surface area in embodiments of the present invention, used nitrogen absorption under low temperature device ソ ー プ ト マ チ ッ Network-1800 (カ Le ロ エ Le バ society system), by multipoint method, calculates.
As the carbon black used in embodiments of the present invention, for example can enumerate, thermally oxidized black system, furnace black system, dim system, thermal black system, Ketjen black system, the black system of naphthalene etc., they can contain two or more.Wherein, can particularly preferably use the carbon black of furnace black system, dim system, there is if the carbon black of the characteristic of the expectation shown in above-mentioned, can use general commercially available black color black.
The thermoplastic resin composition of embodiments of the present invention can further be contained (C) inorganic fill material, can make the physical strength of products formed, dimensional performance improve.As the inorganic fill material, for example can enumerate glass fibre, silica fiber, silica-alumina fiber, Zirconium oxide fibre, boron nitride fibre, silicon nitride fiber, boron fibre, potassium titanate fiber, aluminum borate fiber, wollastonite, quartz powder, pure aluminium silicate, kaolin, granulated glass sphere, glass sphere, glass flake, silicon-dioxide, calcium carbonate, magnesiumcarbonate, titanium oxide, zinc oxide, aluminum oxide, mica, talcum etc.The viewpoint come off from the products formed surface from further inhibition resin combination powder, be preferably mica, talcum etc.In addition, in the fibrous inorganic fill materials such as glass fibre, number average fiber length is preferably the milled fibre of 30～300 μ m.They can contain two or more.
In the thermoplastic resin composition of embodiments of the present invention, the content of inorganic fill material, with respect to total 100 weight parts of above-mentioned thermoplastic resin and above-mentioned carbon black, is preferably 1～200 weight part.Be more than 1 weight part by the content that makes the inorganic fill material, thereby can make the physical strength of products formed, dimensional performance further improve.More preferably more than 10 weight parts.On the other hand, by the content that makes (C) inorganic fill material, be below 200 weight parts, thereby the content of thermoplastic resin improve relatively, can make the physical strength of products formed further improve.More preferably below 120 weight parts.
The thermoplastic resin composition of embodiments of the present invention can be in the scope of not damaging purpose, (for example contain antioxidant and thermo-stabilizer, hindered phenol, quinhydrones, phosphorous acid esters and their replacement body etc.), UV light absorber (for example, Resorcinol, salicylate, benzotriazole, benzophenone etc.), releasing agent (for example, montanic acid and its salt, its ester, its half ester, stearyl alcohol, stearylamide and polyethylene wax etc.), softening agent, fire retardant, flame retardant, the common additive such as static inhibitor, other thermoplastic resin (for example, fluoro-resin etc.) give the characteristic of regulation.
The thermoplastic resin composition of embodiments of the present invention can be by for example, above-mentioned thermoplastic resin and above-mentioned carbon black and other composition as required carried out to melting mixing and obtain.As the method for carrying out melting mixing, for example can enumerate, use Banbury mixer, rubber-roller machine, kneader, single shaft or biaxial extruder etc., carry out the method for melting mixing the temperature of 200～350 ℃.In embodiments of the present invention, for the maximum particle diameter that makes the carbon black in the thermoplastic resin composition is below 50 μ m, preferably by biaxial extruder, carry out melting mixing.As biaxial extruder, equidirectional rotary, rotary the two of different directions can both be used.The melting mixing temperature is preferably the fusing point (Tm) ± 10 ℃ of each thermoplastic resin described later.
In order to make carbon black differential in the thermoplastic resin composition loose, preferably, with respect to the total length (L) from raw material input position (L0) to drain position of biaxial extruder, making the residence time (residence time at initial stage) from raw material input position (L0) to the thermoplastic resin composition between 3L/10 of thermoplastic resin and carbon black is below 15% of the residence time of biaxial extruder total length (total holdup time).Thus, can suppress the aggegation that the solid compressed each other by carbon black in biaxial extruder causes, easily differential is loose.More specifically, preferably at thermoplastic resin during the state in not melting, reduce the setting of elongated kneading disk of residence time at initial stage etc., preferably between L0 to 3L/10, will arrange as main body with respect to extruding the thread screw that direction is positive dirction.Here, the residence time at initial stage in embodiments of the present invention can arrange the cylinder (open vent) with peristome above the position by the 3L/10 at biaxial extruder, measures from raw material and drops into and start to obtain to the time of arrival of open vent.In addition, the total holdup time can start to obtain to the time of discharging the thermoplastic resin composition from the forcing machine front end by measuring from the raw material input.
In addition, preferably, from 3L/10 to the so-called kneading part between drain position, the multi-disc kneading disk is set.About the maximum shear speed in kneading part, from mixing and make the microdispersed viewpoint of carbon black fully, be preferably 1000 more than (/ second), more preferably 2000 (/ second) more than.On the other hand, suppress the viewpoint of the decomposition of the compositions such as thermoplastic resin from suppressing the heating caused by shearing, be preferably below 10000 (/ seconds), below more preferably 8000 (/ seconds).Here, above-mentioned maximum shear speed (/ second) can be calculated by following formula by minimum clearance S (mm) and the screw speed n (rpm) of cylinder inside diameter D (mm), an inwall and the kneading disk of forcing machine.
γmax＝D×n×π/(60×S)
In addition, the minimum clearance S (mm) that the maximum shear speed in kneading part can be by cylinder inwall and kneading disk or screw speed n (rpm) etc., easily be adjusted to desired scope.
The add-on when content of carbon black, inorganic fill material and other additive in the liquid crystalline polyester resin composition obtained by above method is generally manufactured with liquid crystalline polyester resin composition is consistent.
The thermoplastic resin composition of embodiments of the present invention can be carried out to moulding by the known method of forming, thereby obtain various products formeds.For example, can be for various gears, various housings, sensor, the LED parts, the liquid crystal backlight bobbin, junctor, socket, resistor, casing of relay, roll and base for rly., switch, coil bobbin, electrical condenser, the variable condenser housing, optical pickup unit, syntonizer, various terminal strips, transformer, plug, printed wiring board, tuner, loud speaker, microphone, head type headphones, pony pump, head base, power model, shell, semi-conductor, liquid crystal display component, the FDD carriage, the FDD chassis, hdd unit, motor brush holder, parabolic antenna, computer associated components etc. are the electrical and electronic parts of representative, with the VTR parts, TV part (plasma body, organic EL, liquid crystal), flatiron, hair dryer, the electric cooker parts, microwave oven component, sound part, audio frequency, laser disk, the speech ciphering equipment parts such as CD, illuminace component, parts of refrigerator, conditioner parts etc. are the family of representative, enterprise's electric product parts, with the office computer associated components, the telephone set associated components, the facsimile recorder associated components, the duplicating machine associated components, the washing fixture, oilless bearing, stern bearing, the various bearings such as water centre bearer, motor component, lighter for ignition, the mechanical associated components that type-writer etc. are representative, microscope, binoculars, camera, the optical device that clock and watch etc. are representative, the precision optical machinery associated components, the alternator terminal, the alternator junctor, the IC setter, dimmer potentiometer base, the various valves such as exhaust air valve, fuel is relevant, exhaust system, the various pipes of air-breathing system, inlet mouth nozzle ventpipe, intake manifold, petrolift, the engine cool water swivel, the vaporizer main body, the vaporizer spacer, the exhaust gas sensor, the water coolant sensor, oil temperature sensor, throttle position sensor, crankshaft position sensor, air flowmeter, Brake pad abrasion sensor, conditioner thermostatted base, conditioner electric motor isolator, warmer heated airflow control valve, scatterer electric motor brush carrier, water pump impeller, turbine blade, the wiper motor associated components, ignition distributor, starter switch, starter relay, the transmission mechanism bunch, window cleaning device nozzle, the air-conditioner panel switch substrate, the associated magnetic valve coil of fuel, the safety fuse junctor, the ECU junctor, the loudspeaker terminal, the parts of electric insulcrete, the step-by-step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid shaft, engine oil filter, the automobiles such as portfire housing, vehicle associated components etc.
Especially, the thin wall flow dynamic stability excellence of the liquid crystalline polyester resin composition in the thermoplastic resin composition of embodiments of the present invention, insulativity can be obtained high, therefore suppressed the products formed that the resin combination powder comes off from the products formed surface, be preferred for deceiving chromaticity and require the products formed with the following thinner wall section of wall thickness 0.1mm of insulativity.; be suitable for small-sized electrical and electronic parts; for example, thin space junctor, ECU junctor, switch, coil bobbin for pony pump, the camera that uses in parts, portable phone, Digital camera etc. for rly. parts for module, coverture and circumferential component thereof etc. for LED.
Embodiment
Below, by embodiment, effect of the present invention is described in further detail.
The compositional analysis of liquid crystalline polyester and evaluating characteristics are undertaken by following method.
(1) compositional analysis of liquid crystalline polyester
The compositional analysis of liquid crystalline polyester passes through
1The H-NMR (Nuclear Magnetic Resonance) spectrum (
1H-NMR) measure and implement.By in liquid crystalline polyester weighing 50mg to NMR sample tube, be dissolved in solvent (Pentafluorophenol/sym.-tetrachloroethane-d
2=65/35 (weight ratio) mixed solvent), in 800 μ L, use UNITY INOVA500 type NMR device (バ リ ア Application society system), at observing frequency 500MHz, 80 ℃ of enforcements of temperature
1H-NMR measures, by near the peak area that derives from each structural unit observed 7～9.5ppm recently analysis bank become.
(2) mensuration of the fusing point of liquid crystalline polyester (Tm)
In the differential calorimetry, after the observation of the endotherm peak temperature (Tm1) observed when liquid crystalline polyester resin is measured from room temperature under the Elevated Temperature Conditions of 40 ℃/minute, after the temperature of Tm1+20 ℃ keeps 5 minutes, temporarily be cooled to room temperature under the cooling conditions of 20 ℃/minute, the endotherm peak temperature (Tm2) observed while again measuring under the Elevated Temperature Conditions of 20 ℃/minute is made as fusing point (Tm).
(3) melt viscosity of liquid crystalline polyester is measured
Use high formula fluidity test machine CFT-500D (aperture 0.5 φ * 10mm) (Shimadzu Seisakusho Ltd.'s system), the fusing point that is liquid crystalline polyester in temperature+10 ℃, velocity of shear is measured in 1000/ second.
Thermoplastic resin
N6: eastern レ (strain) CM1010 processed (nylon 6)
PBT: eastern レ (strain) 1100S processed (polybutylene terephthalate)
PPS: eastern レ (strain) M3910 processed (polyphenylene sulfide)
Using (A) as thermoplastic resin liquid crystalline polyester resin of using in each embodiment and comparative example, (B) carbon black, (C) talcum, (D) glass fibre and (E) mica and (X) the melting mixing condition in biaxial extruder is shown below.
(A) liquid crystalline polyester resin
Synthesizing of ［ reference example 1 ］ liquid crystalline polyester resin (A-1)
Possessing agitating vane, distillate in the reaction vessel of 5L of pipe and add P-hydroxybenzoic acid 870g (6.30 moles), 4,4 '-dihydroxybiphenyl 327g (1.89 moles), quinhydrones 89g (0.81 mole), terephthalic acid 292g (1.76 moles), m-phthalic acid 157g (0.95 mole) and diacetyl oxide 1367g (1.03 equivalents that the phenol hydroxyl adds up to), after 2 hours, with 4 hours, be warming up to 320 ℃ while stirring 145 ℃ of reactions under nitrogen atmosphere.Then, polymerization temperature is remained on to 320 ℃, be decompressed to 1.0mmHg (133Pa) with 1.0 hours, then continue reaction in 90 minutes, stir after needed torque reaches 15kgcm polycondensation is completed.Next 1.0kg/cm will be forced in reaction vessel
2(0.1MPa), via the mouth mould of the circular row outlet with 1 diameter 10mm, polymkeric substance is discharged to thing into strips, granulated by cutting machine, thereby obtain liquid crystalline polyester resin (A-1).
This liquid crystalline polyester resin (A-1) is carried out to compositional analysis.Liquid crystalline polyester resin (A-1) possesses aminobenzoic acid ester units (structural unit (I)), 4,4 '-dioxy base biphenyl unit (structural unit (II)), Isosorbide-5-Nitrae-dioxy base benzene unit (structural unit (III)), terephthalate units (structural unit (IV)) and m-phthalic acid ester units (structural unit (V)).Liquid crystalline polyester resin (A-1) is with respect to aminobenzoic acid ester units (structural unit (I)), 4, the total of 4 '-dioxy base biphenyl unit (structural unit (II)) and Isosorbide-5-Nitrae-dioxy base benzene unit (structural unit (III)) contain 70 % by mole to aminobenzoic acid ester units (structural unit (I)).In addition, with respect to 4, the total of 4 '-dioxy base biphenyl unit (structural unit (II)) and Isosorbide-5-Nitrae-dioxy base benzene unit (structural unit (III)) contain 70 % by mole 4,4 '-dioxy base biphenyl unit (structural unit (II)).In addition, the terephthalate units (structural unit (IV)) that contains 65 % by mole with respect to the total of terephthalate units (structural unit (IV)) and m-phthalic acid ester units (structural unit (V)).In addition, 4, the total of 4 '-dioxy base biphenyl unit (structural unit (II)) and Isosorbide-5-Nitrae-dioxy base benzene unit (structural unit (III)) is 23 % by mole with respect to the entire infrastructure unit.The total of terephthalate units (structural unit (IV)) and m-phthalic acid ester units (structural unit (V)) is 23 % by mole with respect to the entire infrastructure unit.The fusing point (Tm) of liquid crystalline polyester resin (A-1) is 314 ℃.Use high formula fluidity test machine (aperture 0.5 φ * 10mm), 324 ℃ of temperature, velocity of shear 1, measuring the melt viscosity obtained under 000/s is 20Pas.
Synthesizing of ［ reference example 2 ］ liquid crystalline polyester resin (A-2)
By P-hydroxybenzoic acid 994g (7.20 moles), 4, the polyethylene terephthalate 159g (1.13 moles) that 4 '-dihydroxybiphenyl 126g (0.68 mole), terephthalic acid 112g (0.68 mole), limiting viscosity are about 0.6dl/g and diacetyl oxide 960g (1.10 equivalents that the phenol hydroxyl adds up to) are added in aggregation container, be warming up to 150 ℃ while stirring under nitrogen atmosphere, react 3 hours.Be warming up to 250 ℃ through 2 hours from 150 ℃, through 1.5 hours from 250 ℃ are warming up to 330 ℃, at 325 ℃, within 1.5 hours, to be decompressed to 1.0mmHg (133Pa), then continue to stir 0.25 hour, stir after needed torque reaches 12kgcm polycondensation is completed.Next 1.0kg/cm will be forced in reaction vessel
2(0.1MPa), via the mouth mould of the circular row outlet with 1 diameter 10mm, polymkeric substance is discharged to thing into strips, granulated by cutting machine, thereby obtain liquid crystalline polyester resin (A-2).
This liquid crystalline polyester resin (A-2) is carried out to compositional analysis, result has 66.7 % by mole of aminobenzoic acid ester units (structural unit (I)), 4,4 '-dioxy base biphenyl unit (16.6 % by mole of 6.3 % by mole of structural units (II), 10.4 % by mole of ethylidene dioxy base unit that derive from polyethylene terephthalate, terephthalate units (structural unit (IV)).Fusing point (Tm) is 314 ℃.Use high formula fluidity test machine (aperture 0.5 φ * 10mm), 324 ℃ of temperature, velocity of shear 1, measuring the melt viscosity obtained under 000/s is 25Pas.
Synthesizing of ［ reference example 3 ］ liquid crystalline polyester resin (A-3)
According to Japanese kokai publication sho 54-77691 communique, will be added to acetoxy-benzoic acid 921 weight parts and 6-acetoxyl group-naphthoic acid 435 weight parts and possess agitating vane, distillate in the reaction vessel of pipe, carry out polycondensation.The liquid crystalline polyester resin of gained (A-3) has by structural unit (structural unit (I)) 57 molar equivalents that acetoxy-benzoic acid is generated and structural unit 22 molar equivalents that generated by 6-acetoxyl group-naphthoic acid.Fusing point (Tm) is 283 ℃.Use high formula fluidity test machine (aperture 0.5 φ * 10mm), 293 ℃ of temperature, velocity of shear 1, measuring the melt viscosity obtained under 000/s is 30Pas.
(B) carbon black
(B-1): エ ボ ニ ッ Network デ グ サ ジ ャ パ Application (strain) system " LampBlack101 " (primary particle size 95nm DBP absorbed dose/primary particle size 1.23 (ml/100gnm) BET specific surface area 20 (m
2/ g) dim system)
(B-2): エ ボ ニ ッ Network デ グ サ ジ ャ パ Application (strain) system " HIBLACK170 " (primary particle size 75nm DBP absorbed dose/primary particle size 1.07 (ml/100gnm) BET specific surface area 23 (m
2/ g) furnace black system)
(B-3): コ ロ Application PVC ヤ ン カ ー ボ Application (strain) system " Raven22 " (primary particle size 83nmDBP absorbed dose/primary particle size 1.38 (ml/100gnm) BET specific surface area 28 (m
2/ g) furnace black system)
(B-4): system " #25 " (primary particle size 47nm DBP absorbed dose/primary particle size 1.47 (ml/100gnm) BET specific surface area 55 (m of Mitsubishi Chemical's (strain)
2/ g) furnace black system)
(B-5): コ ロ Application PVC ヤ ン カ ー ボ Application (strain) system " Raven14 " (primary particle size 55nm DBP absorbed dose/primary particle size 2.02BET specific surface area 44 (m
2/ g) dim system)
(C) glass fibre
(C-1): NEG (strain) system " chopped strand ECS03T-747H " (number average fiber length 3.0mm, the equal Fibre diameter 10.5 μ m of number)
(C-2): NEG (strain) system " milled fibre EPG70M-01N " (number average fiber length 70 μ m, the equal Fibre diameter 9 μ m of number)
(D) talcum
(D-1): the タ of Fuji Le Network (strain) system " NK64 " (median diameter 19 μ m)
(E) mica
(E-1): ヤ マ グ チ マ イ カ (strain) makes " A-41 " (median size 43 μ m)
(X) the melting mixing condition in biaxial extruder
(X-1): the screw rod that uses diameter 57.2mm in the biaxial extruder of the middle interpolation mouth of having of cylinder internal diameter 58mm, residence time at initial stage from the raw material supplying mouth (L0) of thermoplastic resin and carbon black to the thermoplastic resin composition between 3L/10 is made as to 10% of the total holdup time, screw speed is made as to 450rpm, by the maximum shear Speed Setting of kneading part, it was 3414 (/ seconds), the barrel design temperature is set as to the fusing point of thermoplastic resin+10 ℃, carries out melting mixing.In addition, contain the material of filling material and added by centre interpolation mouthful, thus acquisition thermoplastic resin composition's particle.In addition, the maximum shear speed of kneading part (/ second) is calculated by following formula by minimum clearance S (mm) and the screw speed n (rpm) of cylinder inside diameter D (mm), cylinder inwall and the kneading disk of forcing machine.
γmax＝D×n×π/(60×S)
(X-2): use the biaxial extruder identical with X-1, residence time at initial stage from the raw material supplying mouth (L0) of thermoplastic resin and carbon black to the thermoplastic resin composition between 3L/10 is made as to 20% of the total holdup time, screw speed is made as to 450rpm, by the maximum shear Speed Setting of kneading part, it was 3414 (/ seconds), the barrel design temperature is set as to the fusing point of thermoplastic resin+10 ℃, carries out melting mixing.In addition, contain the material of filling material and added by centre interpolation mouthful, thus acquisition thermoplastic resin composition's particle.
Use above-mentioned (A) liquid crystalline polyester resin, (B) carbon black and (C) talcum as required, (D) glass fibre and (E) mica, produce the liquid crystalline polyester resin composition of embodiment and comparative example.The characteristic of each liquid crystalline polyester resin composition adopts following method to estimate.
(1) maximum particle diameter of carbon black
Use opticmicroscope, the thermoplastic resin composition's grain section obtained by each embodiment and comparative example with 500～1000 times of observations of multiplying power adds up to 10cm
2.The diameter of the maximum particle in the offspring of the carbon black that mensuration is observed, be made as maximum particle diameter.In addition, the situation for indistinguishable state in the observation at 1000 times, be made as<10 μ m.
(2) insulativity
The thermoplastic resin composition that use is obtained by each embodiment and comparative example, in the situation that liquid crystalline polyester resin composition, by Sodic TR30EHA ((strain) ソ デ ィ ッ Network プ ラ ス テ ッ Network system), injection speed is set as to 500 (mm/ seconds), by mold temperature be set as the fusing point of liquid crystalline polyester resin+20 (℃), the thin-walled test film shown in continuously shaped Fig. 1 (test film thickness 0.10mm, length 50mm, width 5.0mm).The thin-walled test film of the continuously shaped thickness 0.30mm of thermoplastic resin composition except liquid crystalline polyester resin composition, length 50mm, width 5.0mm.Thin-walled test film 1000 about gained is penetrated part, near the cast gate (G1) of test film, central authorities, fill 3 places of end respectively with the coating of the size shown in Fig. 2 conductive paste (Teng Cang changes into (strain) system " De ー タ イ ト (registered trademark) ").Use insulating-resistance meter to measure the resistance of the thickness direction of the test film that is coated with conductive paste, in 1000 penetrate total 3000 places at part * 3 places, calculating resistance value is the spot number formulary of the following resistance of 1000M Ω.It is preferably few that resistance value becomes the following place of 1000M Ω, but as long as the following place of 1000M Ω is 50 to sentence down, can be practical uses no problemly.
(3) thin wall flow dynamic stability
The thermoplastic resin composition that use is obtained by each embodiment and comparative example, in the situation that liquid crystalline polyester resin composition, by Sodic TR30EHA ((strain) ソ デ ィ ッ Network プ ラ ス テ ッ Network system), injection speed is set as to 400 (mm/ seconds), by mold temperature be set as the fusing point of liquid crystalline polyester resin+20 (℃), 50 penetrate the thin-walled test film shown in continuously shaped Fig. 1, estimate the poor of the maximum fluidity length of test film of gained and minimal flow length.In the situation that the thermoplastic resin composition except liquid crystalline polyester resin composition, 50 penetrate the thin-walled test film of continuously shaped thickness 0.30mm, length 50mm, width 5.0mm, estimate the poor of the maximum fluidity length of test film of gained and minimal flow length.The difference of maximum fluidity length and minimal flow length is less, and inhomogeneous fewer, the thin wall flow dynamic stability is more excellent, and the random ejaculation while meaning injection molding is few.Test film random often ejaculation when injection molding that the difference of maximum fluidity length and minimal flow length surpasses 2.0mm occurs.
(4) the resin combination powder evaluation that comes off
Thermoplastic resin composition's particle that use is obtained by each embodiment and comparative example, adopt and estimate identical method with insulativity, produces the thin-walled test film shown in Fig. 1.The thin-walled test film of gained is fed in pure water 200ml, and with 40kHz, 60 seconds ultrasonic washings are implemented in the output of 100W.The membrane filter of diameter 30mm, aperture 1.0 μ m for pure water 200ml after ultrasonic washing is filtered, measure the number of the residue thing on strainer.By the residue thing be less than 10 average evaluation for " good " (◎), by the average evaluations of 10～30, be " well " zero, by the average evaluation over 30, be " poor " (*).
About using already described (A) liquid crystalline polyester resin, (B) carbon black and (C) talcum as required, (D) glass fibre and (E) mica and the embodiment 1～26 that makes and each liquid crystalline polyester resin composition of comparative example 1～14 below describe.
Embodiment 1～26, comparative example 1～14
With respect to thermoplastic resin 100 weight parts shown in table 1～2, (B) carbon black, (C) inorganic fill material are coordinated with the ratio shown in table 1～2, carry out melting mixing according to the melting mixing condition shown in table 1～2, thereby obtain thermoplastic resin composition's particle.Carry out maximum particle diameter, insulativity, the thin wall flow dynamic stability of carbon black, the evaluation of resin combination deciduous by aforesaid method.The results are shown in table 1～2.
[table 1]
[table 2]
Fig. 3 means the observation by light microscope photo by the grain section of embodiment 1 acquisition.Fig. 3 (b) amplifies by the part of Fig. 3 (a) figure obtained, and takes with 1 calibration 50 μ m the photo obtained respectively.Confirmed not observe the particle of carbon black.Fig. 4 means the observation by light microscope photo by the grain section of comparative example 1 acquisition.Fig. 4 (b) amplifies by the part of Fig. 4 (a) figure obtained, and takes with 1 calibration 100 μ m the photo obtained respectively.Confirmed that carbon black (B-2) exists in a large number with the particle diameter that surpasses 50 μ m.
As can be known from the above results, the products formed obtained by thermoplastic resin composition of the present invention is compared with the products formed obtained by comparative example, in requiring the purposes of black, insulativity, thin wall flow dynamic stability excellence, can also suppress the resin combination powder and come off from the products formed surface.
The industry utilizability
Thermoplastic resin composition's of the present invention thin wall flow dynamic stability excellence, bad in the time of can reducing the moulding such as random ejaculation.In addition, the products formed formed by them is due to the insulativity excellence, coming off of resin combination powder in assembling procedure etc. reduced, therefore can be suitable for deceiving chromaticity and requiring insulativity, there is the products formed of thinner wall section, small-sized electrical and electronic parts, for example, thin space junctor, ECU junctor, switch, coil bobbin for pony pump, the camera that uses in parts, portable phone, Digital camera etc. for rly. parts for module, coverture and circumferential component thereof etc. for LED.
The explanation of symbol
The G1 cast gate
B-2 carbon black agglomeration.
Claims (9)
1. a thermoplastic resin composition, is characterized in that, is the thermoplastic resin composition who coordinates carbon black 0.1～20 weight part to form with respect to thermoplastic resin 100 weight parts, and described carbon black is to be dispersed in the thermoplastic resin composition below maximum particle diameter 50 μ m.
2. thermoplastic resin composition according to claim 1, it is characterized in that, the primary particle size of described carbon black is 70～200nm, and the DBP absorbed dose a1 (ml/100g) of carbon black and the ratio a1/a2 of primary particle size a2 (nm) are 0.5～1.5 (ml/100gnm).
3. thermoplastic resin composition according to claim 1 and 2, the specific surface area recorded by BET formula low-temperature nitrogen adsorption method of described carbon black is 10～40 (m
2/ g).
4. according to the described thermoplastic resin composition of any one of claim 1～3, it is characterized in that, described thermoplastic resin is for forming the liquid crystalline polyester resin of anisotropy melting phase.
5. thermoplastic resin composition according to claim 4, it is characterized in that, described liquid crystalline polyester resin forms by following structural unit (I), (II), (III), (IV) with (V), structural unit (I) with respect to structural unit (I), (II) and (III) add up to 65～80 % by mole, structural unit (II) with respect to structural unit (II) and (III) add up to 55～85 % by mole, structural unit (IV) with respect to structural unit (IV) and (V) add up to 50～95 % by mole
6. according to the described thermoplastic resin composition of any one of claim 1～5, its 100 weight parts of total with respect to described thermoplastic resin and described carbon black, also be combined with inorganic fill material 1～200 weight part.
7. the described thermoplastic resin composition's of any one of claim 1～6 manufacture method, to be supplied to major general's thermoplastic resin and carbon black the manufacture method that biaxial extruder carries out the thermoplastic resin composition of melting mixing, it is characterized in that, the overall length (L) from raw material input position (L0) to drain position with respect to biaxial extruder, what make thermoplastic resin and carbon black is below 15% of the residence time of biaxial extruder overall length (total holdup time) from dropping into position (L0) to the residence time between 3L/10 (residence time at initial stage), and making from 3L/10 to the maximum shear speed between drain position is 1000～10000/ seconds, carry out melting mixing.
8. a products formed, the described thermoplastic resin composition's moulding of its any one by claim 1～6 obtains.
9. products formed according to claim 8, it has the following part of wall thickness 0.1mm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP067018/2011 | 2011-03-25 | ||
| JP2011067018 | 2011-03-25 | ||
| PCT/JP2011/006992 WO2012131829A1 (en) | 2011-03-25 | 2011-12-14 | Thermoplastic resin composition and molded article using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103429660A true CN103429660A (en) | 2013-12-04 |
| CN103429660B CN103429660B (en) | 2015-05-27 |
Family
ID=46929672
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180069344.2A Active CN103429660B (en) | 2011-03-25 | 2011-12-14 | Thermoplastic resin composition and molded article using same |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US9947433B2 (en) |
| EP (1) | EP2690140B1 (en) |
| JP (1) | JP5206903B2 (en) |
| KR (1) | KR101413835B1 (en) |
| CN (1) | CN103429660B (en) |
| TW (1) | TWI422627B (en) |
| WO (1) | WO2012131829A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109689795A (en) * | 2016-09-14 | 2019-04-26 | 住友化学株式会社 | Liquid crystalline resin composition |
| CN111989368A (en) * | 2018-04-27 | 2020-11-24 | 住友化学株式会社 | Liquid crystal polyester composition and molded article |
| CN114507419A (en) * | 2020-11-16 | 2022-05-17 | 金发科技股份有限公司 | Liquid crystal polymer composition and preparation method thereof |
| CN116438245A (en) * | 2020-10-29 | 2023-07-14 | 大塚化学株式会社 | Liquid crystal polymer composition, liquid crystal polymer molded body, and electric and electronic device |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2935515B1 (en) | 2012-12-19 | 2020-04-15 | Ticona LLC | Liquid crystalline composition having a dark black color |
| WO2015094486A1 (en) | 2013-12-19 | 2015-06-25 | Ticona Llc | Liquid crystalline composition having a pearly luster |
| JP6400861B2 (en) * | 2016-07-11 | 2018-10-03 | ポリプラスチックス株式会社 | Liquid crystalline resin composition |
| WO2018105624A1 (en) | 2016-12-05 | 2018-06-14 | 株式会社村田製作所 | Black liquid crystal polymer film and multilayer substrate |
| US11722759B2 (en) | 2019-03-20 | 2023-08-08 | Ticona Llc | Actuator assembly for a camera module |
| EP3738749A1 (en) * | 2019-05-17 | 2020-11-18 | Ricoh Company, Ltd. | Thermoplastic resin powder, resin powder, resin powder for producing three-dimensional object, three-dimensional object and three-dimensional object producing method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1265696A (en) * | 1997-06-06 | 2000-09-06 | 伊斯曼化学公司 | Liquid crystalline polyester compositions containing carbon black |
| JP2009179763A (en) * | 2008-01-31 | 2009-08-13 | Toray Ind Inc | Liquid crystal resin composition, method of manufacturing the same and molded article |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4161470A (en) | 1977-10-20 | 1979-07-17 | Celanese Corporation | Polyester of 6-hydroxy-2-naphthoic acid and para-hydroxy benzoic acid capable of readily undergoing melt processing |
| JPS6155146A (en) | 1984-08-24 | 1986-03-19 | Dainichi Seika Kogyo Kk | Composition for pigmented polyamide molding |
| US4728698A (en) * | 1985-09-06 | 1988-03-01 | University Of Akron | Liquid crystal fiber-reinforced polymer composite and process for preparing same |
| JPS62119008A (en) * | 1985-11-20 | 1987-05-30 | Diafoil Co Ltd | Preparation of polyester raw material containing carbon black |
| CA1319241C (en) * | 1987-09-09 | 1993-06-22 | Bernard John Lyons | Conductive polymer composition |
| JP3362489B2 (en) | 1993-12-28 | 2003-01-07 | 東レ株式会社 | Liquid crystalline resin composition and molded article |
| JP3690059B2 (en) * | 1996-05-13 | 2005-08-31 | 東レ株式会社 | Thermoplastic resin composition and molded article |
| JP2000230120A (en) | 1998-12-10 | 2000-08-22 | Toray Ind Inc | Polyphenylene sulfide resin composition |
| JP2000281885A (en) * | 1999-03-31 | 2000-10-10 | Toray Ind Inc | Liquid crystalline resin composition for antistatic use |
| JP2001279066A (en) | 2000-03-31 | 2001-10-10 | Sumitomo Chem Co Ltd | Liquid crystal polyester resin composition |
| DE10112394A1 (en) * | 2001-03-13 | 2002-10-02 | Ticona Gmbh | Conductive plastic molding compound, its use and molded articles made therefrom |
| DE60219853T2 (en) * | 2001-07-18 | 2008-01-17 | Mitsubishi Engineering-Plastics Corp. | Thermoplastic resin composition |
| WO2005012411A1 (en) | 2003-07-29 | 2005-02-10 | The University Of Akron | Electrically-conducting polymers, a method for preparing electrically-conducting polymers, and a method for controlling electrical conductivity of polymers |
| JP2007131774A (en) * | 2005-11-11 | 2007-05-31 | Sumitomo Rubber Ind Ltd | Resin composition |
| KR101353100B1 (en) * | 2006-02-13 | 2014-01-17 | 스미또모 가가꾸 가부시키가이샤 | Liquid-crystalline polymer composition, method for producing the same, and molded article using the same |
| JP5216230B2 (en) * | 2007-03-29 | 2013-06-19 | Ｊｘ日鉱日石エネルギー株式会社 | Conductive resin composition |
| JP5951167B2 (en) | 2008-03-28 | 2016-07-13 | Ｊｘエネルギー株式会社 | Liquid crystalline polyester resin composition for camera modules |
| JP2011089111A (en) * | 2009-09-25 | 2011-05-06 | Toray Ind Inc | Biaxially oriented polyarylene sulfide film |
| JP2011157422A (en) * | 2010-01-29 | 2011-08-18 | Sumitomo Chemical Co Ltd | Liquid crystalline polyester composition, method for producing the same, and connector |
-
2011
- 2011-12-14 JP JP2012506034A patent/JP5206903B2/en active Active
- 2011-12-14 CN CN201180069344.2A patent/CN103429660B/en active Active
- 2011-12-14 EP EP11862614.2A patent/EP2690140B1/en active Active
- 2011-12-14 KR KR1020137025042A patent/KR101413835B1/en active IP Right Grant
- 2011-12-14 WO PCT/JP2011/006992 patent/WO2012131829A1/en active Application Filing
- 2011-12-14 US US14/006,798 patent/US9947433B2/en active Active
- 2011-12-15 TW TW100146516A patent/TWI422627B/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1265696A (en) * | 1997-06-06 | 2000-09-06 | 伊斯曼化学公司 | Liquid crystalline polyester compositions containing carbon black |
| JP2009179763A (en) * | 2008-01-31 | 2009-08-13 | Toray Ind Inc | Liquid crystal resin composition, method of manufacturing the same and molded article |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109689795A (en) * | 2016-09-14 | 2019-04-26 | 住友化学株式会社 | Liquid crystalline resin composition |
| CN111989368A (en) * | 2018-04-27 | 2020-11-24 | 住友化学株式会社 | Liquid crystal polyester composition and molded article |
| CN111989368B (en) * | 2018-04-27 | 2022-11-22 | 住友化学株式会社 | Liquid crystal polyester composition and molded article |
| CN116438245A (en) * | 2020-10-29 | 2023-07-14 | 大塚化学株式会社 | Liquid crystal polymer composition, liquid crystal polymer molded body, and electric and electronic device |
| CN114507419A (en) * | 2020-11-16 | 2022-05-17 | 金发科技股份有限公司 | Liquid crystal polymer composition and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20130117886A (en) | 2013-10-28 |
| US9947433B2 (en) | 2018-04-17 |
| TWI422627B (en) | 2014-01-11 |
| EP2690140A1 (en) | 2014-01-29 |
| CN103429660B (en) | 2015-05-27 |
| TW201239020A (en) | 2012-10-01 |
| EP2690140A4 (en) | 2014-09-17 |
| WO2012131829A1 (en) | 2012-10-04 |
| KR101413835B1 (en) | 2014-06-30 |
| US20140011011A1 (en) | 2014-01-09 |
| JP5206903B2 (en) | 2013-06-12 |
| EP2690140B1 (en) | 2016-11-16 |
| JPWO2012131829A1 (en) | 2014-07-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103429660B (en) | Thermoplastic resin composition and molded article using same | |
| CN101418113B (en) | Liquid crystalline polyester composition | |
| CN102822273B (en) | Liquid-crystalline polyester resin composition, method for producing same, and molded article made thereof | |
| US9045621B2 (en) | Liquid crystalline polyester composition and metal composite molded product using the same | |
| TWI425038B (en) | Liquid crystalline polyester resin composition and metal composite molded article using same | |
| CN109790361A (en) | The manufacturing method of liquid crystalline polyester resin composition, molded product and molded product | |
| JP2019065263A (en) | Liquid crystalline polyester resin composition and molded article formed of the same | |
| WO2018230195A1 (en) | Liquid crystalline polyester resin composition and molded article produced therefrom | |
| JP5262138B2 (en) | Liquid crystalline resin composition and method for producing the same | |
| JP2017082158A (en) | Liquid crystalline polyester resin composition and molding comprising the same | |
| JP2007169379A (en) | Wholly aromatic liquid crystal polyester and composition thereof | |
| JP2015063641A (en) | Liquid crystalline polyester resin composition and molded article comprising the same | |
| JP3562122B2 (en) | Glass bead reinforced liquid crystalline resin composition | |
| JP6255978B2 (en) | Liquid crystalline polyester resin composition and metal composite molded article using the same | |
| JP2009249536A (en) | Liquid-crystalline resin injection-molding compound and method for producing the same | |
| JP2008074899A (en) | Method for producing liquid crystalline resin | |
| JP4066526B2 (en) | Liquid crystalline resin and thermoplastic resin composition | |
| WO2022191099A1 (en) | Liquid crystal resin composition, and molded article comprising same | |
| JP2000191755A (en) | Production of liquid-crystalline resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |